Research Article www.acsami.org
Tunable Ultrathin Membranes with Nonvolatile Pore Shape Memory Hidenori Kuroki,† Crescent Islam,† Igor Tokarev,† Heng Hu,§ Guojun Liu,§ and Sergiy Minko*,†,‡ †
Department of Chemistry and Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States Nanostructured Materials Lab, University of Georgia, Athens, Georgia 30602, United States § Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6, Canada ‡
S Supporting Information *
ABSTRACT: The concept of a responsive nanoporous thin-film gel membranes whose pores could be tuned to a desired size by a specific “molecular signal” and whose pore geometry becomes “memorized” by the gel is reported. The ∼100 nm thick membranes were prepared by dip-coating from a solution mixture of a random copolymer comprising responsive and photo-cross-linkable units and monodisperse latex nanoparticles used as a sacrificial colloidal template. After stabilization of the films by photo-cross-linking the latex template was removed, yielding nanoporous structures with a narrow pore size distribution and a high porosity. The thin-film membranes could be transferred onto porous supports to serve as tunable size-selective barriers in various colloids separation applications. The pore dimensions and hence the membrane’s colloidal-particle-size cutoff were reversibly regulated by swelling− shrinking of the polymer network with a specially selected low-molar-mass compound. The attained pore shape was “memorized” in aqueous media and “erased” by treatment in special solvents reverting the membrane to the original state. KEYWORDS: nanostructure, responsive membrane, pore memory, template, size-selective filtration
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INTRODUCTION Stimuli-responsive membranes,1−3 which exhibit changes in the pore geometry in response to external stimuli, such as temperature,4−9 pH,10−13 light,14 magnetic field,15 oxidation− reduction state,16,17 specific ions,18,19 chemical reagents,20,21 or proteins,22,23 can regulate the transport of small molecules, particles, proteins, viruses, and cells via the pore gating triggered by the stimuli. Most of the stimuli-responsive membranes have been prepared via grafting of responsive polymers on pore walls of multimicrometer-thick filtration membranes. The relatively thick selective layers of such membranes possess a high hydrodynamic resistance. Recently, a number of studies have focused on the development of stimuli-responsive membranes using various thin (typically, less than 1 μm) porous platforms24 prepared by lithography techniques,25−27 focused ion beam etching,28 phase-separation of block copolymer thin films,29−36 and templating with colloidal particles,37−39 cross-linked nanoparticles40 or proteins.41 Such thin membranes have a much lower hydrodynamic resistance and small cross-sectional dimensions appropriate for various applications from membrane-based separation technologies to miniaturized devices. In our previous publications, we have demonstrated responsive gel thin-film membranes (in a thickness range of 100−200 nm) with two− dimensionally arranged pores using simple phase separation methods.42−45 Their pore size can be varied in the range of 200 nm to 1 μm at the open state. Furthermore, the pore geometry (size and shape) of the responsive membranes can be tuned by applying external stimuli (e.g., pH change and interactions with specially selected low-molecular-weight substances), due to © 2015 American Chemical Society
swelling and shrinking of the entire membrane. The dynamically changeable pore−geometries provide a unique opportunity for the regulation of mass transport through the membrane, thus, enabling design of novel smart systems for various applications, such as flow control, size−selective filtration, chemical and biological separations, controlled release of chemical substances and drugs, chemical sensors, and biosensors. In addition to the smart dynamic systems whose pore geometries are sensitive to the changeable membrane’s environment, another property of stimuli-responsive membranes valuable for practical applications would be the ability to adjust and then stiffen the demanded pore geometry. The pore size adjustment could be conducted in the first step by changing the membrane environment. Then, the membrane could be “frozen” at the desired state in the second step. The porous membrane of this kind could be used as a universal platform for various applications when the pore size could be adjusted and memorized by the membrane. This membrane property is named here nonvolatile pore shape memory. A method for the stabilization of pore geometry of porous films with adjustable nonvolatile pore shape memory, introduced in this article, is demonstrated using a colloidal template membrane as an example. However, the introduced concept could be applied for membranes prepared using different fabrication methods when the pores are adjusted and stabilized Received: February 18, 2015 Accepted: April 26, 2015 Published: April 27, 2015 10401
DOI: 10.1021/acsami.5b01416 ACS Appl. Mater. Interfaces 2015, 7, 10401−10406
Research Article
ACS Applied Materials & Interfaces
Figure 1. Schematic (a and b) and corresponding AFM topological images (c and d) of the nanostructured P(2VP-co-CEA) gel membrane, prepared by the template method: (a and c) The gel film with embedded PS latex particles on the substrate. (b and d) The gel membrane with uniform pore sizes formed after dissolution of the latex template. (e) The pore size distribution estimated from the AFM image (d). (f) Cross-sectional SEM image of the membrane (after removal of the latex template and prior to plasma treatment) with a zoomed-in area (g). visualization of fractured regions using a high resolution field emission scanning electron microscope (FE-SEM, JSM-7400, JEOL). The gold nanoparticles (AuNPs) with positively−charged surfaces were synthesized by the previously reported method.48 The particle size was found to be 32 ± 7 nm by the AFM analysis of a monolayer of the particles adsorbed onto a Si substrate. For the demonstration of nanoparticle transport through the pores, the membranes were immersed in the AuNP solution at pH 7.2 for 3 h, and then washed with DI water (pH 5.5) five times. The resulting membranes were dried in a N2 gas flow and analyzed with AFM to identify the locations of adsorbed AuNPs.
with a reversible physically cross-linked network that provides pore shape memory.
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EXPERIMENTAL SECTION
The nanoporous responsive gel membranes were fabricated via a colloidal template method. A copolymer of P(2VP-co-CEA) (P2VP:PCEA = 80:20 mol %, Mn = 68,000 g mol−1, Mw/Mn = 1.8), which was synthesized using the free radical polymerization (see the Supporting Information for details), and 210 nm monodisperse polystyrene (PS) latex particles from Invitrogen life technologies were used. A 4 wt % aqueous dispersion of PS latex nanoparticles (pH 5.5) was added dropwise to an 8 wt % P(2VP-co-CEA) solution (pH 2.0) while sonicating until a volume ratio of 1:1 was reached. After additional sonication for 30 min, the mixture was deposited by dipcoating on Si or glass substrates under low humidity (
Tunable Ultrathin Membranes with Nonvolatile Pore Shape Memory Hidenori Kuroki,† Crescent Islam,† Igor Tokarev,† Heng Hu,§ Guojun Liu,§ and Sergiy Minko*,†,‡ †
Department of Chemistry and Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States Nanostructured Materials Lab, University of Georgia, Athens, Georgia 30602, United States § Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6, Canada ‡
S Supporting Information *
ABSTRACT: The concept of a responsive nanoporous thin-film gel membranes whose pores could be tuned to a desired size by a specific “molecular signal” and whose pore geometry becomes “memorized” by the gel is reported. The ∼100 nm thick membranes were prepared by dip-coating from a solution mixture of a random copolymer comprising responsive and photo-cross-linkable units and monodisperse latex nanoparticles used as a sacrificial colloidal template. After stabilization of the films by photo-cross-linking the latex template was removed, yielding nanoporous structures with a narrow pore size distribution and a high porosity. The thin-film membranes could be transferred onto porous supports to serve as tunable size-selective barriers in various colloids separation applications. The pore dimensions and hence the membrane’s colloidal-particle-size cutoff were reversibly regulated by swelling− shrinking of the polymer network with a specially selected low-molar-mass compound. The attained pore shape was “memorized” in aqueous media and “erased” by treatment in special solvents reverting the membrane to the original state. KEYWORDS: nanostructure, responsive membrane, pore memory, template, size-selective filtration
■
INTRODUCTION Stimuli-responsive membranes,1−3 which exhibit changes in the pore geometry in response to external stimuli, such as temperature,4−9 pH,10−13 light,14 magnetic field,15 oxidation− reduction state,16,17 specific ions,18,19 chemical reagents,20,21 or proteins,22,23 can regulate the transport of small molecules, particles, proteins, viruses, and cells via the pore gating triggered by the stimuli. Most of the stimuli-responsive membranes have been prepared via grafting of responsive polymers on pore walls of multimicrometer-thick filtration membranes. The relatively thick selective layers of such membranes possess a high hydrodynamic resistance. Recently, a number of studies have focused on the development of stimuli-responsive membranes using various thin (typically, less than 1 μm) porous platforms24 prepared by lithography techniques,25−27 focused ion beam etching,28 phase-separation of block copolymer thin films,29−36 and templating with colloidal particles,37−39 cross-linked nanoparticles40 or proteins.41 Such thin membranes have a much lower hydrodynamic resistance and small cross-sectional dimensions appropriate for various applications from membrane-based separation technologies to miniaturized devices. In our previous publications, we have demonstrated responsive gel thin-film membranes (in a thickness range of 100−200 nm) with two− dimensionally arranged pores using simple phase separation methods.42−45 Their pore size can be varied in the range of 200 nm to 1 μm at the open state. Furthermore, the pore geometry (size and shape) of the responsive membranes can be tuned by applying external stimuli (e.g., pH change and interactions with specially selected low-molecular-weight substances), due to © 2015 American Chemical Society
swelling and shrinking of the entire membrane. The dynamically changeable pore−geometries provide a unique opportunity for the regulation of mass transport through the membrane, thus, enabling design of novel smart systems for various applications, such as flow control, size−selective filtration, chemical and biological separations, controlled release of chemical substances and drugs, chemical sensors, and biosensors. In addition to the smart dynamic systems whose pore geometries are sensitive to the changeable membrane’s environment, another property of stimuli-responsive membranes valuable for practical applications would be the ability to adjust and then stiffen the demanded pore geometry. The pore size adjustment could be conducted in the first step by changing the membrane environment. Then, the membrane could be “frozen” at the desired state in the second step. The porous membrane of this kind could be used as a universal platform for various applications when the pore size could be adjusted and memorized by the membrane. This membrane property is named here nonvolatile pore shape memory. A method for the stabilization of pore geometry of porous films with adjustable nonvolatile pore shape memory, introduced in this article, is demonstrated using a colloidal template membrane as an example. However, the introduced concept could be applied for membranes prepared using different fabrication methods when the pores are adjusted and stabilized Received: February 18, 2015 Accepted: April 26, 2015 Published: April 27, 2015 10401
DOI: 10.1021/acsami.5b01416 ACS Appl. Mater. Interfaces 2015, 7, 10401−10406
Research Article
ACS Applied Materials & Interfaces
Figure 1. Schematic (a and b) and corresponding AFM topological images (c and d) of the nanostructured P(2VP-co-CEA) gel membrane, prepared by the template method: (a and c) The gel film with embedded PS latex particles on the substrate. (b and d) The gel membrane with uniform pore sizes formed after dissolution of the latex template. (e) The pore size distribution estimated from the AFM image (d). (f) Cross-sectional SEM image of the membrane (after removal of the latex template and prior to plasma treatment) with a zoomed-in area (g). visualization of fractured regions using a high resolution field emission scanning electron microscope (FE-SEM, JSM-7400, JEOL). The gold nanoparticles (AuNPs) with positively−charged surfaces were synthesized by the previously reported method.48 The particle size was found to be 32 ± 7 nm by the AFM analysis of a monolayer of the particles adsorbed onto a Si substrate. For the demonstration of nanoparticle transport through the pores, the membranes were immersed in the AuNP solution at pH 7.2 for 3 h, and then washed with DI water (pH 5.5) five times. The resulting membranes were dried in a N2 gas flow and analyzed with AFM to identify the locations of adsorbed AuNPs.
with a reversible physically cross-linked network that provides pore shape memory.
■
EXPERIMENTAL SECTION
The nanoporous responsive gel membranes were fabricated via a colloidal template method. A copolymer of P(2VP-co-CEA) (P2VP:PCEA = 80:20 mol %, Mn = 68,000 g mol−1, Mw/Mn = 1.8), which was synthesized using the free radical polymerization (see the Supporting Information for details), and 210 nm monodisperse polystyrene (PS) latex particles from Invitrogen life technologies were used. A 4 wt % aqueous dispersion of PS latex nanoparticles (pH 5.5) was added dropwise to an 8 wt % P(2VP-co-CEA) solution (pH 2.0) while sonicating until a volume ratio of 1:1 was reached. After additional sonication for 30 min, the mixture was deposited by dipcoating on Si or glass substrates under low humidity (
